Acid monoazo dyestuffs



United States Patent ice ACID MONOAZO DYESTUFFS Franz Frisch, Arlesheim,Switzerland, assignor to Sandoz A. G., Basel, Switzerland, a Swiss firmNo Drawing. Application August 21, 1952, Serial No. 305,685

Claims priority, application Switzerland August 28, 1951 6 Claims. (Cl.260-194) The present invention relates to acid monoazo dyestuffs whichcorrespond to the formula s o,H H035 NHaey1 wherein acyl stands for theradical of a saturated aliphatic acid containing at least 8 and at most12 carbon atoms, one y stands for hydrogen or lower alkyl, the other ystanding for hydrogen or lower alkyl or-in the case where the one y ishydrogen-forming with the adjacent x the saturated hydrocarbon chain andwherein xin the case where both ys are hydrogen or lower alkyl-standsfor hydrogen, halogen, alkyl, lower alkoxy, NH-acyl, SO2-alkyl,SO2-aralkyl, -SO2-ary1, SOz-cycloalkyl SO2-Oaryl, OSOz-alkyl,O40z-aralkyl or OSO2-aryl, the alkyl being lower alkyl throughout.

The aforesaid acid monoazo dyestufls can be prepared by coupling a diazocompound of an aminobenzene sulfonic acid of the formula SOaH wherein xand y have the precedingly-indicated significances, with a1-hydroxynaphthalene-3-sulfonic acid of the formula HO S NH-acy1 whereinacyl also has the precedingly-recited significances.

Suitable aminobenzene sulfonic acids of Formula II comprise inter aliathe following:

1-aminobenzene-2-sulfonic acid;

l-amino-5-chlorobenzcne2-sulfonic acid;1-amino-S-brornobenzene-Z-sulfonic acid;1-amino-S-methylbenzene-Z-sulfonic acid;l-amino-S-ethylbenzene-Z-sulfonic acid;l-amino-S-methoxybenzene-Z-sulfonic acid;1-amino-S-ethoxybenzene-Z-srflfonic acid;1-amino-5-propoxybenzene-Z-sulfonic acid;l-amino-S-N-formylaminobenzene-Z-sulfonic acid;1-amino-S-N-acetylaminobenzene-Z-sulfonic acid;1-amino-5-N-propionylaminobenzene-2-sulfonic acid;1-amino-5-N-benzoylaminobenzene-Z-sulfonic acid; 1 amino 5 Nchlorobenzoylaminobenzene 2 sulfonic acid; 1 amino 5 Nbromobenzoylaminobenzene 2 sulfonic acid;1-amino-5-methylsulfonbenzene-Z-sulfonic acid;1-amino-5-ethylsulfonbenzene-Z-sxflfonic acid;1-amino-5-propylsulfonbenzene-2-sulfonic acid;l-amino-5-benzylsulfonbenzene-Z-sulfonic acid;1-amino-S-phenylsulfonbenzeneZ-sulfonic acid; l-amino-S-(methyl)-phenylsulfonbenzene-2-sulfonic acid;l-amino-S-(chloro)-phenylsulfonbenzene-Z-sulfonic acid; 1 amino 5(dimethyl) phenylsulfonbenzene 2 sulfonic acid;l-amino-5-cyclohexylsulfonbenzene-2-sulfonic acid;1-amino-2-su1fobenzene-5-sulfonic acid-N-methylamide;l-amino-2-sulfobenzene-5-sulfonic acid-N-ethylamide;1-amino-Z-sulfobenzene-S-sulfonic acid-N-propylamide; 1 amino 2sulfohenzene 5 sulfonic acid N cyclohexylarnide;1-amino-2-sulfobenzene-S-sulfonic acid-N-phenylamide; 1 amino 2sulfobenzene 5 sulfonic acid N (methyl)-phenylamide;1-amino-2-sulfobenzene-5-su1fonic acid-N-(chloro)-phenylamide; 1 amino 2sulfobenzene 5 sulfonic acid N (dimethyD-phenylamide; 1 amino 2sulfobenzene 5 sulfonic acid N,N

dimethylamide; 1 amino 2 sulfobenzene 5 sulfonic acid N,N

diethylamide; 1 amino 2 sulfobenzene 5 sulfonic acid N,N

dipropylamide; l amino 2 sulfobenzene 5 sulfonic acid N,N

dibutylamide; 1 amino 2 sulfobenzene 5 sulfonic acid N,N

methylphenylamide; 1-amino-2-sulfobenzene-S-sulfonic ylamide;1-amino-Z-sulfobenzene-S-sulfonic acid-N,N-propyl-phenylamide;l-amino-Z-sulfobenzene-S-sulfonic ylamide;1-amino-2-su1fobenzene-5-sulfonic zylamide;1-amin0-2-sulfo-benzene-5-sulfonic acid-N,N-ethyl-bcnzylamide;1-amino-2-sulfobenzene-5 sulfonic acid-N,N-propyl-benzylamide;

acid-N,N-ethyl-phenacid-N,N-butyl-phenacid-N,N-methyl-ben-1-amino-2-sulfobenzene-5-sulfonic acid-N,N-butyI-benzylamide;

1-amino-2-sulfobenzene5-sulfonic acid-N,N-methyl-cyclohexylamide;

l-amino-2-sulfobenzene-5-sulfonic acid-N,N-ethyl-cyclohexylamide;

l amino 2 sulfobenzene 5 sulfonic acid N,N

propyl-cyclohexylamide;

1-amino-2-sulfobenzene-5-su1fonic acid-N,N-butyl-cyclohexylamide;

1 amino 2 sulfobenzene 5 sulfonic acid N,N

benzyl-cyclohexylamide;

l-amino-Z-sulfobenzene-S-sulfonic acid-phenyl ester;

1-amino-i-sulfobenzene-fi-sulfonic acid-(methyl)-phenyl ester;1-amino-2-sulfobenzene-5-sulfonic acid-(chloro)-phenyl ester; 71-amino-2-sulfobeiiZene-S-suIfonic acid-(dimethylj-phenyl ester;1-amino-5-methylrsulfonyl oirybnzene-2-sulfonic acid;1-arnino-5-ethyl-sulfonyl-oxybenzene-Z-suItQnic acid; 1-amino-5-prof ylsulfonyl-oirybenzene 2-sulfonic acid; 1-amino-5-butylsiilfoi1yl-oXybenzeneQ-sulfonic acid;1-amino-5-benayl-sulfonyl-oxybenzene-Z-sulfonic acid; 1-amino 5-pheiiylsulfonyl-oXybenzene 2-sulfonic acid; 1 amino i 5 (methyl) phenylsulfonyl oxyben- Zeii'eQZ-suIfonie acid; W Y p p H l no 5 7 (chloro)phenyl sulfonyl oxybenzene 2-s1ilf6iiic acid; 1 amino -.5 -,(dimethy1)phenyl sulfonyl oxyben- "zen 2 siilfonic acid; ?d m thY1b n @n-2:su!t nicid 1-amino-4,6 dimethylbenzene- 2-spltonic acid; h iflii il fi -2;$i4 fa as qa. 1-amino-4-riithyLS-chlorobenzene-2 sulfonic acid, etc.

Suitable ammohennene sulf onic acids wherein the saturated hydr'dcarbon7 chain gc rikcrn cn cgrninterconnects the positions x andj are forexample l aniino-5,6,7,8-tetra y ronaphthalene-Z-sulfonic acid and2-amihb 5,6,7,8-tetiahydronaphthalene-3 -sul fonie 7 acid.

Illustrative of suitable 1 hydroxynaphtlialene 3 sultpnic acids ofFormula III are inter alia 1 -hy droxy-6 -N-pctanoi i iai -3- u i9 d J'q 9 TTN canoylarriinohaphthalene-3-sulfonic acid, 1 hydroxy-6-N-dodecanoylarninonaphthalene-3-sulfonic acid, etc. w p The coupling ofthe diazo compound of the amino- .benzene sulfonic acid of Formula IIwith the il -hydro xyjiaph'thaIeiie 3-sulfoi1ic acid of Formula III iseffected in 'weak alkaline to weak acid (acetic acid) medium,adyantageously in the presence of sodium bicarbonate or sodium acetate.Upon completion of the coupling, the formed dyestufi-insofar as it hasnot precipitated-'45 salted out, filtered OE, and dried. V V p I W pthus-obtained dyestufls, according to the present invention, dissolvewith orange-red coloration wafer and dye, wool, silk vand other animalfibers, as well, as polyamide fibers such for example as nylon, from aneutral or weak acidbath in bright orange shades of very good fastnessto light and of good fastness to perspiraficnm tQ h n e t The fdll'ovifig -e iiafnples are illustrative, but not limitativ e, of theinvention. The .parts are by weighg'aild the temperatures are in degreeseemi'graire.

Exahzple 1 173 parts of 1'-aminobenzene-2-sulfonic acid -are dissolvedin 50 parts of cold water and 100 parts of normal aqueons sodium,hydroxide 7 solution, and then a solution of 7 parts of sodium nitritein 50 parts of water is added -By, theaddition of, ice, the temperatureis br'ough't to 5-10. While stirring, 30 parts of concentrated hydrochlorig acid are then added at one time, and'stirring is continuedat 10-15 until the nitrous acid disappears. The formed'diazo compoundseparatesout in part;

The suspension of the diazo compound is combined a solution of 58.6parts of the sodium salt at -1'-hydroxy-S-N-octanoylaminonaphthalene-3-sulfonic acid in 1 00 0 partsotwater at 10-15" in the presence of -20 parts of sodium bicarbonate. H Mj Upon completion of the coupling, the resultant dyestufi whichcorresponds to the formula "m e'o enai-en,

4 i powder which dissolves with orange coloration in water and dyeswool, silk and nylon from a weak acid bath iii bright orange shades ofgood fastness to washing and to perspiration and of very good fastnessto light.

Dyestuffs with similar properties are obtained when, in preparing theaforementioned diazo compound, the l-aminobenzene-Z-sulfonic acid isreplaced by an equivalent quantity of 1-amino-5 chlorobiiieii 2 sulfonicacid or of l-amino5bromobenZene-2-sulfonic acid oi of 1-amino-S-methylbenzene-2-sulfonic acid or of l-amino-S-ethylbenzene-Z-sulfonic acid or of l-amino-S-methoxyto the formula is"salted out, filtered bit and dried. It is an orange} 'doloi ed powderwhich dissolves with orange coloration in hot water and dyes wool, sillz and nylon in bright yellowish orange shades of good fastness towashing and to perspiration and of very good fastness to light.

DyestuHsIwith similar properties are obtained when, in preparing thediazo compound accordingto the preceding paragraph, the lamino-5-methylsulfOnbenzene-Z-sultonic acid. is replaced by anequivalent quantity of 1- amino-5-ethylsulfonbenzene-Z-sulfonic acid orof l-amino- 5-propylsulfonbeiazene-Z-sulfonic acid or of l-amino-5-benzylsulfonbenzene-2-sulfonic acid or of l-amino-S-phenylsulfonbenzene-Z-sulfonic acid or of 1-amino-5-(4'-methylphenyl)-sulfonbenzene-Z-sulfonic acid or of 1-amino-S-(4'-chlorophenyl) sulfonbenzenb-Z-sulfonic acid or of l-amin02=sulfobenzene-S-sulfonic acid-N-phenylamide or-of1amino-2-sulfobenzene-5-sulfonic acid-N- (2'-,4- dimethyl)'-ph enylamideor of l-amino-Z-ulfobenzene-S- sulfonic acid N,N-dimethylamide or ofl-amino-2-sulfobenzene- 5-sulfonic acid-N,N-diethylamide I) v,

Similar properties are also possessed by the dyestufi of the formularin-cot'cnan om obtainable, according to the method of the present e15-ample, from diazotized 1-arnino-S-chlorobenzene-Lsul fonic acid and1-hydroxy-6-decanoylaminonaphthalene- 3-sulfonic acid. k

Example 3 acetate at 10-1S. Upon completion of the coupling, theprecipitated dyestutf which corresponds to the formula tam-Q 0H I 30 11HO: NH-C O-(CHDto-CH;

is filtered ofi and dried. It is an orange-colored powder whichdissolves with orange coloration in hot water and dyes wool, silk andnylon from a neutral or weak acid bath in yellowish orange shades ofvery good fastness to washing, perspiration and light.

Dyestuffs with similar properties are obtained when, in preparing thediazo suspension according to the preceding paragraph, thel-amino-2-sulfonbenzene-5-sulfonic acid-phenylester is replaced by anequivalent quantity of 1-amino-5-methylsulfonyl-oxybenzene-Z-sulfonicacid or of 1-amino-5-ethylsulfonyl-oxybenzene-Z-sulfonic acid or of1-amino-5-butylsulfonyl-oxybenzene-2-sulfonic acid or of1-amino-5-benzylsulfonyl-oxybenzene-Z-sulfonic acid or oflamino--phenylsulfonyl-oxybenzene-Z-sulfonic acid or ofl-amino-S-(2',4-dimethylphenyl) -sulfonyl-oxybenzene-Z-sulfonic acid. orof 1-amino-5-(4'-methylphenyl)-sulfonyl-oxybenzene-2- sulfonic acid orof 1- amino-5-(4'-chlorophenyl)-sulfonly-oxybenzene 2 sulfonic acid. Thelatter corresponds to the formula HOG-c1 O NH: SiO;H

Example 4 SOgH H0 8 is filtered oil and dried. It is an orange-coloredpowder which dissolves with orange coloration in hot water and dyeswool, silk and nylon in bright orange shades of good fastness to washingand perspiration and of very good fastness to light.

Dyestufis with similar properties are obtained when, while otherwiseproceeding according to the preceding aragraph, thel-hydroxy-6-N-decanoylaminonaphthalene-3-sulfonic acid is replaced by anequivalent quantity of 1 hydroxy-6-N-dodecanoylaminonaphthalene 3sulfonic acid, and/or the l-aminobenzene-Z-sulfonic acid, used inpreparing the diazo compound, is replaced by an equivalent quantity of1arnino-2-sulfobenzene-S-sulfonic acid-N,N-methyl-benzylamide or ofl-amino-Z-sulfobenzene-S-sulfonic acid-N,N-ethyl-benzylamide or of 1-amino-Z-sulfobenzene-S-sulfonic acid N,N methylcyclohexylamide or ofl-amino 2-sulfobenzene-S-sulfonic acid- N,N-ethyl-cyclohexylamide orof1-amino-2-sulfobenzene- S-sulfonic acid-N,N-benzyl-cyclohexylamide.

The dyestufi from diazotized 1-aminobenzene-2- sul-- fonic acid andl-hydroxy-6-N-dodecanoylaminonaphthalene-3-sulfonic acid corresponds tothe formula Example 5 SOz-CH; OH

OgH HO3S- NHCO(CH2)10OH;

is filtered 0E and dried. It is an orange-colored powder which dissolveswith orange coloration in hot water and dyes wool, silk and nylon inbright yellowish orange shades of good fastuess to washing and toperspiration and of very good fastness to light.

Dyestuffs with similar properties are obtained when, while otherwiseproceeding according to the preceding paragraph, the1-hydroxy-6-N-dodecanoylaminonaphthalene-3-sulfonic acid is replaced byan equivalent amount of 1-hydroxy-6-N-ootanoylaminonaphthalene-.i-sulfonic acid and/or the 1-amino-5-methylsulfonbenzene-Z-sulfonicacid, used in preparing the diazo compound, is replaced by an equivalentamount of l-amino- S-ethylsulfonbenzene-Z-sulfonic acid or of l-amino-S-butylsulfonbenzene-2-sulfonic acid or of l-amino-S-chlorobenzene-3-sulfonic acid or of l-amino-S-bromobenzene-Z-sulf-onicacid or of 'l-amino-5-me'thylbenzene- 2-sulfonic acid or of1-amino-5-ethylbenzene 2-sulfonic acid.

Example 6 I 11 HOgS is salted out, filtered oil and dried. It is anorangecolored powder which dissolves with orange coloration in hot waterand dyes wool, silk and nylon from a Weak acetic acid bath in brightorange shades of good fastness 'to washing and to perspiration and ofvery good fastness to light.

A dyestufi with similar properties is obtained when, while otherwiseproceeding as described in the preceding paragraph, the1-hydroXy=6-N-decanoylaminonaphthalene-3-sulfonic acid used for thecoupling, is replaced :by an equivalent amount ofl-hydroXy-6-N-dodecanoylaminonaphthalene-B-sulfonic acid and/or thel-amino- 5-N-acetylaminobenzene-2 sulfonic acid, used in preparing thediazo compound, is replaced by an equivalent amount of 1-amino-5-N-butyrylamino'benzene-Z-sulfonic 7 acid or of l arhino--Nbenzoylamiiiobniene-2=siilfofiic acid. I

Example7 22.2 par-ts of 1-amino-4 methyl-5 chloroberizerie-Z-sulfonicacid are diazotized, after the manner described in Example 1, and theresultant aqueous suspension of diazo compound is combined with asuspehsion of 38.6 parts of 1-hydroxy6-N-octanoylaminonaphthalene-3-sulfonic acid in 1500 parts of water inthe presence of an excess of sodium bicarbonate at 1045". Uponcompletion of the coupling, the precipitated dyestuff, correspondnigtothe formula is filtered ofl and dried. It is an orange-colored powderwhich dissolves with orange coloration in hot water and dyes Wool, silkand nylon from a weak acid bath in bright orange shades of goodfastne'ss to washing and to perspiration and of very good fastness tolight.

Example 8 is filtered off and dried. It is an orange-colored powderwhich dissolves with orange coloration in hot water and dyes wool, silkand nylon in bright reddish orange shades of good fas tness to washingand to perspiration and of very good fastness to light. I

A similar dyestuff is obtained when, in the foregoing, the2-ainino-5,6,7,8 tetrahydronaphthalene3-sulfoiiic acid is replaced bythe corresponding quantity of l amino-5;6,7,8-tetrahydronaphthalene-2=sulfohic acid.

Example 9 20.1 parts of 1-amino-4,5-dimethylbenzene 2-sulfonic acid arediazotized, after the manner described in Example 1, and the resultantsuspension of diazo compound is combined with a suspension of 42 partsof -1-hydr0xy- 6-N-dodecanoylarninonaphthalene-3sulfonic acid in 1500parts of Water in the presence of an excess of sodium bicarbonate at10-15"; Upon completion of the coupling, the precipitated dyestufi whichcorresponds to the formula OH, OH

I c HON=N A dystiifi with sii'ifiliir'prop'ei'ties is obtained when, inthe aforesaid diazeeempeuad, the l-afiiind-4,S-dimethylbenzeneQ-sulfonic acid is replaced by an equivalent quantityof 1-amino-4,=dimethylbenzene-Z- sulfonic acid or of1=amino-4,6-dietliylbenzene 2-si1lfonic acid.

Example 10 1 part of a dyestutf according to any one of Examples 1 to 9,10 parts of sodium sulfate and 2 parts of acetic acid are dissolved in8000 par-ts of water. 100 parts of wool are introduced into [thesolution at; 40-50", and the whole then boiled for 30 minutes. Thedyebath is then cooled to and, after the addition of 2 parts of formicacid, again boiled for 30 minutes. The wool, which is thus dyed in afast shade, is rinsed and dried.

A similar result is obtained if the 2 parts of formic acid are replacedby 3 parts of acetic acid. I I 7 Nylon and silk are dyed in like manner,although in the case of silk the boiling is omitted and the bath heatedto 9 O-9Sf. V w

Having thus disclosed the invention, what is claimed is:

1. An acid monoazo dyestutf which corresponds to the formula 2: y OH lwtl wherein acyl stands for the radical of a saturated aliphatic acidcontaining at least 8 and at most 12 carbon atoms, one y stands for amember selected from the group consisting of hydrogen and lower alkyl,the other y fora member selected from the group consisting of hydrogenand lower alkyl andin the case where the one y is hydrogenforms with theadjacent x the saturated hydrocarbon chain CH 2CH2CH2CH2, and whereinxin the case where both ys are hydrogen or lower alkyl'stands for amember selected from the group consisting of hydrogen, chlorine,bromine, lower alkyl, lower NH acyl 3. The acid monoazo dyestuff whichcorresponds to the formula NH-C unease-ca.

4. The acid monoazo dyestufi which corresponds to 6. The acid monoazodyestufi which corresponds to the formula the formula 5. The acidmonoazo dyestufi which corresponds to the formula 10 References Cited inthe file of this patent sol-CE UNITED STATES PATENTS 2,034,247 Reindelet a1. Mar. 17, 1936 2,102,115 Fleischhauer et a1 Dec. 14, 1937 0&1 HONH-CO-(CHOs-CH; 15

1. AN ACID MONOAZO DYESTUFF WHICH CORRESPONDS TO THE FORMULA